EP2913385A1 - Grease composition - Google Patents
Grease composition Download PDFInfo
- Publication number
- EP2913385A1 EP2913385A1 EP13848677.4A EP13848677A EP2913385A1 EP 2913385 A1 EP2913385 A1 EP 2913385A1 EP 13848677 A EP13848677 A EP 13848677A EP 2913385 A1 EP2913385 A1 EP 2913385A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- grease composition
- carbon atoms
- rolling bearings
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004519 grease Substances 0.000 title claims abstract description 70
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 238000005096 rolling process Methods 0.000 claims abstract description 41
- 239000000654 additive Substances 0.000 claims abstract description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 36
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 32
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 32
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 31
- 239000002199 base oil Substances 0.000 claims abstract description 31
- 239000003921 oil Substances 0.000 claims abstract description 29
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 28
- 230000000996 additive effect Effects 0.000 claims abstract description 26
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 26
- 239000003112 inhibitor Substances 0.000 claims abstract description 25
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002562 thickening agent Substances 0.000 claims abstract description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 14
- 239000011701 zinc Substances 0.000 claims description 26
- 150000001412 amines Chemical group 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 13
- -1 diurea compound Chemical class 0.000 claims description 11
- 239000011575 calcium Substances 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 150000007942 carboxylates Chemical class 0.000 claims description 5
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 125000005609 naphthenate group Chemical group 0.000 claims description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- XMKLTEGSALONPH-UHFFFAOYSA-N 1,2,4,5-tetrazinane-3,6-dione Chemical compound O=C1NNC(=O)NN1 XMKLTEGSALONPH-UHFFFAOYSA-N 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 description 24
- 238000005461 lubrication Methods 0.000 description 19
- 229910000831 Steel Inorganic materials 0.000 description 18
- 239000010959 steel Substances 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229920013639 polyalphaolefin Polymers 0.000 description 11
- 230000035515 penetration Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 150000001463 antimony compounds Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 239000010696 ester oil Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000005078 molybdenum compound Substances 0.000 description 4
- 150000002752 molybdenum compounds Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- MKFUUBCXQNCPIP-UHFFFAOYSA-L calcium;2,3-di(nonyl)naphthalene-1-sulfonate Chemical compound [Ca+2].C1=CC=C2C(S([O-])(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1.C1=CC=C2C(S([O-])(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1 MKFUUBCXQNCPIP-UHFFFAOYSA-L 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- WDNQRCVBPNOTNV-UHFFFAOYSA-N dinonylnaphthylsulfonic acid Chemical compound C1=CC=C2C(S(O)(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1 WDNQRCVBPNOTNV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 150000002826 nitrites Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- COGHWIKGZJHSAG-UHFFFAOYSA-L zinc;2,3-di(nonyl)naphthalene-1-sulfonate Chemical compound [Zn+2].C1=CC=C2C(S([O-])(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1.C1=CC=C2C(S([O-])(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1 COGHWIKGZJHSAG-UHFFFAOYSA-L 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- VAMBUGIXOVLJEA-UHFFFAOYSA-N 4-(butylamino)phenol Chemical compound CCCCNC1=CC=C(O)C=C1 VAMBUGIXOVLJEA-UHFFFAOYSA-N 0.000 description 1
- NKFIBMOQAPEKNZ-UHFFFAOYSA-N 5-amino-1h-indole-2-carboxylic acid Chemical compound NC1=CC=C2NC(C(O)=O)=CC2=C1 NKFIBMOQAPEKNZ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XYRMLECORMNZEY-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S XYRMLECORMNZEY-UHFFFAOYSA-B 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- BHPUWVRNNDJLEP-UHFFFAOYSA-K antimony(3+);dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Sb+3].[O-]P([O-])([S-])=S BHPUWVRNNDJLEP-UHFFFAOYSA-K 0.000 description 1
- JZGCHBKDZSRVPQ-UHFFFAOYSA-K antimony(3+);tricarbamodithioate Chemical compound [Sb+3].NC([S-])=S.NC([S-])=S.NC([S-])=S JZGCHBKDZSRVPQ-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- IKXFIBBKEARMLL-UHFFFAOYSA-N triphenoxy(sulfanylidene)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=S)OC1=CC=CC=C1 IKXFIBBKEARMLL-UHFFFAOYSA-N 0.000 description 1
- COTPAMORPWZHKE-UHFFFAOYSA-H trizinc;thiophosphate;thiophosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=O.[O-]P([O-])([O-])=S COTPAMORPWZHKE-UHFFFAOYSA-H 0.000 description 1
- SQOXTAJBVHQIOO-UHFFFAOYSA-L zinc;dicarbamothioate Chemical compound [Zn+2].NC([O-])=S.NC([O-])=S SQOXTAJBVHQIOO-UHFFFAOYSA-L 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/06—Mixtures of thickeners and additives
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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- C—CHEMISTRY; METALLURGY
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
-
- C—CHEMISTRY; METALLURGY
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/0406—Ethers; Acetals; Ortho-esters; Ortho-carbonates used as base material
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/10—Amides of carbonic or haloformic acids
- C10M2215/102—Ureas; Semicarbazides; Allophanates
- C10M2215/1026—Ureas; Semicarbazides; Allophanates used as thickening material
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/02—Bearings
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
- F16C33/30—Parts of ball or roller bearings
- F16C33/66—Special parts or details in view of lubrication
- F16C33/6603—Special parts or details in view of lubrication with grease as lubricant
- F16C33/6633—Grease properties or compositions, e.g. rheological properties
Definitions
- the present invention relates to a grease composition used for rolling bearings of the automotive electrical equipment or automotive auxiliaries.
- the poly-V belts have been employed since the mid-1980s to meet the tendencies toward smaller-diameter pulleys and larger transmission torque, and to improve the belt durability. Concurrently, there has occurred a problem of unexpected early flaking associated with white change in structure on the rolling surface of the rolling bearings.
- the bearings for use in the automotive electrical equipment or automotive auxiliaries have been thus required to have both long lubrication life and excellent resistance to flaking.
- lithium soap greases or diurea greases using as the base oil inexpensive mineral oil
- lithium soap greases or diurea greases using as the base oil a synthetic hydrocarbon oil and an ether type synthetic oil and the like.
- the aromatic urea-containing diurea greases are frequently chosen in light of the durability under high temperatures.
- an anti-flaking additive for example, an oxidizer for passivation such as nitrites or the like is added to the grease composition for oxidizing the metal surface to inhibit the catalytic action thereof, thereby preventing the generation of hydrogen that would be caused by decomposition of the lubricant.
- an anti-flaking additive for example, an oxidizer for passivation such as nitrites or the like is added to the grease composition for oxidizing the metal surface to inhibit the catalytic action thereof, thereby preventing the generation of hydrogen that would be caused by decomposition of the lubricant.
- azo compounds capable of absorbing hydrogen be added to the grease used for metal materials required to have tribological properties and for a variety of members, in particular, to the grease to be enclosed in the bearing located at a portion easily exposed to water ( JP 2002-130301 A ).
- a grease composition comprising a fluorinated polymer oil as the base oil, polytetrafluoroethylene as the thickener, and an electroconductive material is proposed for the purpose of extending the life of rolling bearings, without causing the hydrogen embrittlement-induced flaking even when water permeates through the bearing ( JP 2002-250351 A ).
- a grease composition comprising a poly ⁇ -olefin synthetic oil or diphenyl ether type synthetic oil, a urea-based thickener, at least one of an organic antimony compound or an organic molybdenum compound as the extreme-pressure agent, and zinc sulfonate ( JP 2004-108403 A ), which is designed to form a film on the surface of the rolling bearing to reduce the load applied to the rolling bearing in the tangential direction thereof under severe conditions including high temperatures, high speeds, heavy loads and the like.
- any of the above-mentioned proposals are not sufficient measures to cope with the hydrogen embrittlement because those proposals are not intended to cope with the action after generation of hydrogen, in other words, to prevent the permeation of hydrogen into the inside of metal. Further, the addition of any nitrite, organic antimony compound or organic molybdenum compound is found to decrease the lubrication life at high temperatures.
- An object of the invention is to provide a grease composition for the rolling bearings used for automotive electrical equipment or automotive auxiliaries, which is capable of extending the bearing lubrication life even at elevated temperatures, and preventing hydrogen from penetrating into the inside of metals to exhibit excellent resistance to hydrogen embrittlement-induced flaking.
- the inventors of the invention have successfully solved the problems of the bearing lubrication life at elevated temperatures and the anti-flaking life by choosing a proper base oil, thickener and additives. Namely, the invention provides a grease composition and a rolling bearing for automotive electrical equipment or automotive auxiliaries where the above-mentioned grease composition is enclosed as shown below.
- the grease composition of the invention can exhibit a long lubrication life even at elevated temperatures and excellent anti-flaking properties.
- Fig. 1 is a schematic diagram showing the test using four rolling steel balls.
- n indicates 1500 rpm and W indicates 100 kg (4.1 GPa).
- the base oil that can be used in the invention comprises as an essential component an alkyldiphenyl ether oil that exhibits a sufficient viscosity at high temperatures, less evaporation under high temperatures than ester type oils and poly ⁇ -olefin oils, excellent stability against oxidation, and less production of sludge.
- the alkyl group may be a branched or straight-chain group, and the latter may be preferable.
- the alkyl group may preferably have 10 to 20 carbon atoms, more preferably 12 to 14 carbon atoms.
- One kind of alkyldiphenyl ether oil may be used alone, or two or more kinds may be used in combination.
- the content of the alkyldiphenyl ether oil in the base oil is not particularly limited, but may preferably be 60 mass% or more, and more preferably 100 mass%, based on the total mass of the base oil, to obtain a long life at high temperatures.
- ester type synthetic oils such as diester oils and polyol ester oils
- synthetic hydrocarbon oils such as poly ⁇ -olefin oils, silicone type synthetic oils, and fluorinated synthetic oils
- ester type synthetic oils and the synthetic hydrocarbon oils are preferred, and in particular, dipentaerythritol ester oils and poly ⁇ -olefin oils are preferable.
- the kinematic viscosity of the base oil at 40°C there is no restriction on the kinematic viscosity of the base oil at 40°C, but the kinematic viscosity thereof may preferably be 30 to 300 mm 2 /s, more preferably 50 to 200 mm 2 /s and most preferably 50 to 150 mm 2 /s.
- the kinematic viscosity of the base oil exceeds 300 mm 2 /s at 40°C, the low-temperature flowability will be unsatisfactory.
- the kinematic viscosity of the base oil is less than 30 mm 2 /s at 40°C, the oil tends to easily evaporate and show poor heat resistance.
- the thickener that can be used in the invention is a diurea compound represented by the following formula (1):
- R 2 is a bivalent aromatic hydrocarbon group having 6 to 15 carbon atoms; and one of R 1 or R 3 represents cyclohexyl group and the other represents cyclohexyl group, an alkyl group having 8 to 22 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms.
- R 2 Representative examples of the group indicated by R 2 include the groups having the following structural formulas, and most preferable is a group where two phenyl groups are bonded to methylene group, as indicated in the center.
- alkyl group having 8 to 22 carbon atoms straight-chain alkyl groups having 8 to 18 carbon atoms are preferred, and straight-chain alkyl groups having 18 carbon atoms are most preferable.
- aromatic hydrocarbon group having 6 to 12 carbon atoms those having seven carbon atoms are most preferable.
- the diurea compounds of formula (1) where one of R 1 or R 3 represents cyclohexyl group and the other represents an alkyl group having 8 to 22 carbon atoms are preferable.
- the diurea compounds of formula (1) where one of R 1 or R 3 represents cyclohexyl group and the other represents an aromatic hydrocarbon group having 6 to 12 carbon atoms are also preferable.
- the ratio of the number of moles of the cyclohexyl group which is expressed by [ ⁇ (the number of cyclohexyl groups) / (the number of cyclohexyl groups + the number of alkyl groups) ⁇ x 100] may preferably be 50 mol% or more. If the ratio of the cyclohexyl group in terms of the number of moles is less than 50%, the resultant grease tends to soften and increase the flowability, so that the grease easily leaks from the bearing, which will shorten the life. In light of this, the ratio of the cyclohexyl group in terms of the number of moles may preferably be 50% or more, more preferably 75% or more, and still more preferably 80% or more, and preferably 90% or less.
- R 1 or R 3 represents cyclohexyl group and the other represents an alkyl group having 8 to 22 carbon atoms in formula (1)
- the compound of formula (1) is preferable if R 2 is the group previously indicated in the center, R 1 is cyclohexyl group, and R 3 represents a straight-chain alkyl group having 18 carbon atoms, with the ratio of the cyclohexyl group being 75 to 90 mol%.
- R 1 or R 3 represents cyclohexyl group and the other represents an aromatic hydrocarbon group having 6 to 12 carbon atoms in formula (1)
- the compound of formula (1) is most preferable if R 2 is the group previously indicated in the center, R 1 is cyclohexyl group, and R 3 represents an aromatic hydrocarbon group having 7 carbon atoms.
- the content of the above-mentioned thickener may preferably be in the range of 10 to 25 mass%, and more preferably 13 to 20 mass%, based on the total mass of the grease composition according to the invention. With the content of less than 10 mass%, the resultant grease will be soft and may causes the problem of leakage, which cannot satisfy the lubrication life. On the other hand, when the content exceeds 25 mass%, the poor flowability will hinder the grease from entering into the portions to be lubricated, which may make the lubrication life unsatisfactory.
- the grease composition of the invention is intended to extend the anti-flaking life by using as the anti-flaking additive an organic sulfonate rust inhibitor and a load carrying additive in combination.
- the compounds represented by the following formula (2) may advantageously be used. [R 4 -SO 3 ]n 1 M 1 (2)
- R 4 is an alkyl group, alkenyl group, alkylnaphthyl group, dialkylnaphthyl group, alkylphenyl group or residual group of high-boiling petroleum fraction.
- the above-mentioned alkyl group or alkenyl group is a straight-chain or branched group having 2 to 22 carbon atoms.
- R 4 may be a dialkylnaphthyl group where an alkyl group has 6 to 18 carbon atoms, more preferably 8 to 12 carbon atoms, and most preferably nine carbon atoms.
- M 1 represents an alkali metal, alkaline earth metal, zinc or ammonium ion.
- M 1 preferably represents an alkaline earth metal or zinc.
- alkaline earth metals calcium is preferable.
- n 1 is the valence number of M 1 .
- the organic sulfonate rust inhibitor may be at least one salt selected from the group consisting of zinc salts and calcium salts.
- the organic sulfonate rust inhibitor may preferably be at least one selected from the group consisting of zinc dinonylnaphthalenesulfonate and calcium dinonylnaphthalenesulfonate.
- the content of the organic sulfonate rust inhibitor may preferably be in the range of 0.1 to 10 mass%, and more preferably 0.2 to 5 mass%, based on the total mass of the grease composition according to the invention.
- thiocarbamates such as zinc dialkyldithiocarbamate (ZnDTC) and the like
- thiophosphates such as zinc dialkyldithiophosphate (ZnDTP) and the like
- naphthenates such as zinc naphthenate, calcium naphthenate and the like
- carboxylates such as zinc alkylcarboxylate and the like
- organic phosphate esters such as trioctyl phosphate, triphenylphosphorothionate and the like may be used.
- the load carrying additive may preferably be at least one selected from the group consisting of thiocarbamates, thiophosphates, naphthenates, carboxylates and organic phosphate esters, and more preferably selected from the group consisting of thiocarbamates and thiophosphates.
- the load carrying additive may be an alkali metal salt, alkaline earth metal salt, zinc salt or ammonium salt.
- the zinc salt is preferable.
- the load carrying additive may more preferably be zinc thiocarbamate or zinc thiophosphate, and most preferably zinc dialkyldithiocarbamate or zinc dialkyldithiophosphate.
- the content of the load carrying additive may preferably be 0.1 to 10 mass%, and more preferably 0.2 to 5 mass%, based on the total mass of the grease composition according to the invention.
- the total content of the organic sulfonate rust inhibitor and the load carrying additive may preferably be 0.2 to 20 mass%, and more preferably 0.5 to 10 mass%, based on the total mass of the grease composition according to the invention.
- the grease composition of the invention further comprises an antioxidant.
- the antioxidant may include amine type antioxidants, phenol type antioxidants, and the like. In particular, it is recommendable to use the amine type antioxidant and the phenol type antioxidant in combination because the grease tends to deteriorate by oxidation under the circumstances of high temperatures.
- the amine type antioxidant include alkyldiphenylamine, N-n-butyl-p-aminophenol, ⁇ -naphthylamine, N-phenyl- ⁇ -naphthylamine, phenothiazine and the like.
- alkyldiphenylamine is preferred.
- the phenol type antioxidant may include hindered phenols and the like. In particular, hindered phenol is preferred.
- the total content of the antioxidant may preferably be 0.5 to 6 mass% based on the total mass of the grease composition according to the invention.
- the grease composition of the invention may further comprise other additives, such as other rust inhibitors than the above-mentioned organic sulfonate rust inhibitor, such as amine-based and carboxylate-based rust inhibitors; a metallic corrosion inhibitor such as benzotriazole or the like, an oiliness improver such as fatty acids, fatty acid esters, phosphates and the like; phosphorus-containing, sulfur-containing or organic metal-containing antiwear agent and extreme-pressure agent except the above-mentioned load carrying agent; and a solid lubricant such as oxidized metal salts, molybdenum disulfide or the like.
- the contents of those optional additives may generally be 0.5 to 5 mass% based on the total mass of the grease composition according to the invention.
- the grease composition of the invention may not comprise any nitrite, organic antimony compound or organic molybdenum compound because such compounds contribute to deterioration of the lubrication life at high temperatures.
- the nitrites include sodium nitrite
- the organic antimony compounds include antimony dithiocarbamate and antimony dithiophosphate
- the organic molybdenum compounds include molybdenum dithiocarbamate and molybdenum dithiophosphate.
- the worked penetration of the grease composition according to the invention may preferably be 200 to 300, and more preferably 220 to 280.
- the worked penetration exceeds 300, the high-speed revolutions will often cause the problem of grease leakage, which may hinder the satisfactory lubrication life.
- the worked penetration is less than 200, the poor flowability of the resultant grease may not satisfy the required lubrication life.
- the bearings where the grease composition of the invention is enclosed are rolling bearings for the automotive electrical equipment or automotive auxiliaries, such as alternators, electromagnetic clutches for car's air conditioners, intermediate pulleys, idler pulleys, tension pulleys and the like.
- Diphenylmethane diisocyanate (MDI) was reacted with an amine (cyclohexylamine (CHA), octylamine and p-toluidine in the predetermined amounts) in each base oil and the reaction mixture was diluted with the base oil to have a worked penetration of 280 (when determined according to JIS K2220), thereby obtaining a base grease. Some additives were added to the base grease. Thus, grease compositions were prepared in Examples and Comparative Examples.
- the base oils and additives used in the preparation of the grease compositions are as follows.
- the base oil used in Examples 7 and 17 has a kinematic viscosity at 40°C of 92.8 mm 2 /s: and the base oil used in Examples 8 and 18 has a kinematic viscosity at 40°C of 90.4 mm 2 /s.
- Fig. 1 three steel balls with a diameter of 15 mm designed for bearings were disposed in a cylindrical container with an inner diameter of 40 mm and a height of 14 mm, which was filled with about 20 g of a test grease composition.
- Another steel ball (5/8-in) for bearing was set to a tester so that the steel ball (5/8-in) was placed in contact with the top of the three steel balls.
- the steel ball (5/8-in) was driven to rotate for 4 hours for shakedown with the application of a load in a direction of W as shown in Fig. 1 , and then hydrogen gas was introduced into the tester.
- the lower three balls revolved as each rotating on its axis. The ball was driven to rotate continuously until the flaking took place on the steel ball surfaces.
- the grease compositions of Examples 1 to 20 can exhibit long bearing lubrication life under elevated temperatures, and at the same time excellent resistance to flaking caused by hydrogen embrittlement.
- the grease compositions of Comparative Examples 4, 5, 12 and 13 containing no load carrying additive, and the grease compositions of Comparative Examples 6, 7, 14 and 15 containing no organic sulfonate rust inhibitor are inferior in the resistance to flaking caused by hydrogen embrittlement in any case.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Rolling Contact Bearings (AREA)
Abstract
Description
- The present invention relates to a grease composition used for rolling bearings of the automotive electrical equipment or automotive auxiliaries.
- To satisfy the demands on cars for a smaller size and lighter weight on one hand and a larger living space on the other hand, the reduction of space for the engine room has been required, which has led to the reduction in size and weight of the parts in the automotive electrical equipment and automotive auxiliaries, such as alternators, tension pulleys and the like. Also, in response to the demand for quietness, the engine room is closely sealed, so that greases are required to be resistant to high temperatures in consideration of the high-temperature operating environments.
- In addition, the poly-V belts have been employed since the mid-1980s to meet the tendencies toward smaller-diameter pulleys and larger transmission torque, and to improve the belt durability. Concurrently, there has occurred a problem of unexpected early flaking associated with white change in structure on the rolling surface of the rolling bearings.
- The bearings for use in the automotive electrical equipment or automotive auxiliaries have been thus required to have both long lubrication life and excellent resistance to flaking.
- There are conventionally employed for rolling bearings lithium soap greases or diurea greases using as the base oil inexpensive mineral oil; lithium soap greases or diurea greases using as the base oil a synthetic hydrocarbon oil and an ether type synthetic oil and the like. In particular, the aromatic urea-containing diurea greases are frequently chosen in light of the durability under high temperatures.
- However, those greases cannot satisfy the long bearing life under high temperatures because of the insufficient heat resistance of the employed base oils or thickeners and the poor flowability toward bearing portions to be lubricated with grease.
- In order to inhibit a catalytic action on the metal surface newly exposed as a result of the wear, an anti-flaking additive, for example, an oxidizer for passivation such as nitrites or the like is added to the grease composition for oxidizing the metal surface to inhibit the catalytic action thereof, thereby preventing the generation of hydrogen that would be caused by decomposition of the lubricant. (
JP (Hei) 3-210394 A JP (Hei) 5-263091 JP (Hei) 3-250094 A JP 2002-130301 A JP 2002-250351 A JP 2004-108403 A - However, any of the above-mentioned proposals are not sufficient measures to cope with the hydrogen embrittlement because those proposals are not intended to cope with the action after generation of hydrogen, in other words, to prevent the permeation of hydrogen into the inside of metal. Further, the addition of any nitrite, organic antimony compound or organic molybdenum compound is found to decrease the lubrication life at high temperatures.
- An object of the invention is to provide a grease composition for the rolling bearings used for automotive electrical equipment or automotive auxiliaries, which is capable of extending the bearing lubrication life even at elevated temperatures, and preventing hydrogen from penetrating into the inside of metals to exhibit excellent resistance to hydrogen embrittlement-induced flaking.
- The inventors of the invention have successfully solved the problems of the bearing lubrication life at elevated temperatures and the anti-flaking life by choosing a proper base oil, thickener and additives. Namely, the invention provides a grease composition and a rolling bearing for automotive electrical equipment or automotive auxiliaries where the above-mentioned grease composition is enclosed as shown below.
- 1. A grease composition for rolling bearings of automotive electrical equipment or automotive auxiliaries, comprising;
a base oil that comprises as an essential component an alkyldiphenyl ether oil;
a thickener consisting of a diurea compound represented by the following formula (1):
as an anti-flaking additive an organic sulfonate rust inhibitor and a load carrying additive; and
an antioxidant. - 2. The grease composition for rolling bearings described in the above-mentioned item 1, wherein the thickener is the diurea compound of formula (1) in which one of R1 or R3 represents cyclohexyl group and the other represents an alkyl group having 8 to 22 carbon atoms, with the ratio of the cyclohexyl group in terms of the number of moles being 50 mol% or more when expressed by [{(the number of cyclohexyl groups) / (the number of cyclohexyl groups + the number of alkyl groups)} x 100].
- 3. The grease composition for rolling bearings described in the above-mentioned item 1, wherein the thickener is the diurea compound of formula (1) in which one of R1 or R3 represents cyclohexyl group and the other represents an aromatic hydrocarbon group having 6 to 12 carbon atoms.
- 4. The grease composition for rolling bearings described in any one of the above-mentioned items 1 to 3, wherein the organic sulfonate rust inhibitor is represented by the following formula (2):
[R4-SO3]n1M1 (2)
wherein R4 is an alkyl group, alkenyl group, alkylnaphthyl group, dialkylnaphthyl group, alkylphenyl group or residual group of high-boiling petroleum fraction where the alkyl group or alkenyl group is a straight-chain or branched group having 2 to 22 carbon atoms; M1 is an alkali metal, alkaline earth metal, zinc or ammonium ion; and n1 is the valence number of M1. - 5. The grease composition for rolling bearings described in the above-mentioned item 4, wherein the organic sulfonate rust inhibitor is at least one selected from the group consisting of zinc sulfonate and calcium sulfonate.
- 6. The grease composition for rolling bearings described in any one of the above-mentioned items 1 to 5, wherein the load carrying additive is at least one selected from the group consisting of thiocarbamates, thiophosphates, naphthenates, carboxylates, and organic phosphate esters.
- 7. The grease composition for rolling bearings described in any one of the above-mentioned items 1 to 6, wherein the load carrying additive is at least one selected from the group consisting of zinc dialkyldithiocarbamates and zinc dialkyldithiophosphates.
- 8. The grease composition for rolling bearings described in any one of the above-mentioned items 1 to 7, wherein the antioxidant is an amine type antioxidant and/or a phenol type antioxidant.
- 9. The grease composition for rolling bearings described in the above-mentioned
item 8, wherein the amine type antioxidant is an alkyldiphenylamine and the phenol type antioxidant is a hindered phenol. - 10. A rolling bearing for automotive electrical equipment or automotive auxiliaries, wherein the grease composition described in any one of the above-mentioned items 1 to 9 is enclosed.
- The grease composition of the invention can exhibit a long lubrication life even at elevated temperatures and excellent anti-flaking properties.
-
Fig. 1 is a schematic diagram showing the test using four rolling steel balls. In the figure, n indicates 1500 rpm and W indicates 100 kg (4.1 GPa). - The base oil that can be used in the invention comprises as an essential component an alkyldiphenyl ether oil that exhibits a sufficient viscosity at high temperatures, less evaporation under high temperatures than ester type oils and poly α-olefin oils, excellent stability against oxidation, and less production of sludge. The alkyl group may be a branched or straight-chain group, and the latter may be preferable. The alkyl group may preferably have 10 to 20 carbon atoms, more preferably 12 to 14 carbon atoms. One kind of alkyldiphenyl ether oil may be used alone, or two or more kinds may be used in combination.
- The content of the alkyldiphenyl ether oil in the base oil is not particularly limited, but may preferably be 60 mass% or more, and more preferably 100 mass%, based on the total mass of the base oil, to obtain a long life at high temperatures.
- When the alkyldiphenyl ether oil is used in combination with other base oil components, for example, ester type synthetic oils such as diester oils and polyol ester oils, synthetic hydrocarbon oils such as poly α-olefin oils, silicone type synthetic oils, and fluorinated synthetic oils may be used. Especially, the ester type synthetic oils and the synthetic hydrocarbon oils are preferred, and in particular, dipentaerythritol ester oils and poly α-olefin oils are preferable.
- There is no restriction on the kinematic viscosity of the base oil at 40°C, but the kinematic viscosity thereof may preferably be 30 to 300 mm2/s, more preferably 50 to 200 mm2/s and most preferably 50 to 150 mm2/s. When the kinematic viscosity of the base oil exceeds 300 mm2/s at 40°C, the low-temperature flowability will be unsatisfactory. When the kinematic viscosity of the base oil is less than 30 mm2/s at 40°C, the oil tends to easily evaporate and show poor heat resistance.
- Under the circumstances of high temperatures, the flowability of the grease in the bearing varies depending on the kind of thickener contained in the grease, which has a serious effect on the bearing lubrication life. For obtaining the long lubrication life, the grease is required to constantly retain on the portions to be lubricated, without softening or leakage. In light of this, the thickener that can be used in the invention is a diurea compound represented by the following formula (1):
- In the formula (1), R2 is a bivalent aromatic hydrocarbon group having 6 to 15 carbon atoms; and one of R1 or R3 represents cyclohexyl group and the other represents cyclohexyl group, an alkyl group having 8 to 22 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms.
-
- As the alkyl group having 8 to 22 carbon atoms, straight-chain alkyl groups having 8 to 18 carbon atoms are preferred, and straight-chain alkyl groups having 18 carbon atoms are most preferable. As the aromatic hydrocarbon group having 6 to 12 carbon atoms, those having seven carbon atoms are most preferable.
- The diurea compounds of formula (1) where one of R1 or R3 represents cyclohexyl group and the other represents an alkyl group having 8 to 22 carbon atoms are preferable. The diurea compounds of formula (1) where one of R1 or R3 represents cyclohexyl group and the other represents an aromatic hydrocarbon group having 6 to 12 carbon atoms are also preferable.
- When one of R1 or R3 represents cyclohexyl group and the other represents an alkyl group having 8 to 22 carbon atoms in formula (1), the ratio of the number of moles of the cyclohexyl group, which is expressed by [{(the number of cyclohexyl groups) / (the number of cyclohexyl groups + the number of alkyl groups)} x 100] may preferably be 50 mol% or more. If the ratio of the cyclohexyl group in terms of the number of moles is less than 50%, the resultant grease tends to soften and increase the flowability, so that the grease easily leaks from the bearing, which will shorten the life. In light of this, the ratio of the cyclohexyl group in terms of the number of moles may preferably be 50% or more, more preferably 75% or more, and still more preferably 80% or more, and preferably 90% or less.
- Particularly, in the case where one of R1 or R3 represents cyclohexyl group and the other represents an alkyl group having 8 to 22 carbon atoms in formula (1), the compound of formula (1) is preferable if R2 is the group previously indicated in the center, R1 is cyclohexyl group, and R3 represents a straight-chain alkyl group having 18 carbon atoms, with the ratio of the cyclohexyl group being 75 to 90 mol%.
- In the case where one of R1 or R3 represents cyclohexyl group and the other represents an aromatic hydrocarbon group having 6 to 12 carbon atoms in formula (1), the compound of formula (1) is most preferable if R2 is the group previously indicated in the center, R1 is cyclohexyl group, and R3 represents an aromatic hydrocarbon group having 7 carbon atoms.
- The content of the above-mentioned thickener may preferably be in the range of 10 to 25 mass%, and more preferably 13 to 20 mass%, based on the total mass of the grease composition according to the invention. With the content of less than 10 mass%, the resultant grease will be soft and may causes the problem of leakage, which cannot satisfy the lubrication life. On the other hand, when the content exceeds 25 mass%, the poor flowability will hinder the grease from entering into the portions to be lubricated, which may make the lubrication life unsatisfactory.
- The grease composition of the invention is intended to extend the anti-flaking life by using as the anti-flaking additive an organic sulfonate rust inhibitor and a load carrying additive in combination.
- As the organic sulfonate rust inhibitor, the compounds represented by the following formula (2) may advantageously be used.
[R4-SO3]n1M1 (2)
- In the above formula, R4 is an alkyl group, alkenyl group, alkylnaphthyl group, dialkylnaphthyl group, alkylphenyl group or residual group of high-boiling petroleum fraction. The above-mentioned alkyl group or alkenyl group is a straight-chain or branched group having 2 to 22 carbon atoms. Preferably, R4 may be a dialkylnaphthyl group where an alkyl group has 6 to 18 carbon atoms, more preferably 8 to 12 carbon atoms, and most preferably nine carbon atoms.
- M1 represents an alkali metal, alkaline earth metal, zinc or ammonium ion. In particular, M1 preferably represents an alkaline earth metal or zinc. Of the alkaline earth metals, calcium is preferable.
- In the formula, n1 is the valence number of M1.
- Preferably, the organic sulfonate rust inhibitor may be at least one salt selected from the group consisting of zinc salts and calcium salts. In particular, the organic sulfonate rust inhibitor may preferably be at least one selected from the group consisting of zinc dinonylnaphthalenesulfonate and calcium dinonylnaphthalenesulfonate.
- The content of the organic sulfonate rust inhibitor may preferably be in the range of 0.1 to 10 mass%, and more preferably 0.2 to 5 mass%, based on the total mass of the grease composition according to the invention.
- As the load carrying additive used in the invention, thiocarbamates such as zinc dialkyldithiocarbamate (ZnDTC) and the like, thiophosphates such as zinc dialkyldithiophosphate (ZnDTP) and the like, naphthenates such as zinc naphthenate, calcium naphthenate and the like, carboxylates such as zinc alkylcarboxylate and the like, organic phosphate esters such as trioctyl phosphate, triphenylphosphorothionate and the like may be used.
- The load carrying additive may preferably be at least one selected from the group consisting of thiocarbamates, thiophosphates, naphthenates, carboxylates and organic phosphate esters, and more preferably selected from the group consisting of thiocarbamates and thiophosphates.
- Desirably, the load carrying additive may be an alkali metal salt, alkaline earth metal salt, zinc salt or ammonium salt. Particularly, the zinc salt is preferable.
- In particular, the load carrying additive may more preferably be zinc thiocarbamate or zinc thiophosphate, and most preferably zinc dialkyldithiocarbamate or zinc dialkyldithiophosphate.
- The content of the load carrying additive may preferably be 0.1 to 10 mass%, and more preferably 0.2 to 5 mass%, based on the total mass of the grease composition according to the invention.
- It is particularly preferable to use zinc dinonylnaphthalenesulfonate or calcium dinonylnaphthalenesulfonate as the organic sulfonate rust inhibitor, and ZnDTC or ZnDTP as the load carrying additive.
- The total content of the organic sulfonate rust inhibitor and the load carrying additive may preferably be 0.2 to 20 mass%, and more preferably 0.5 to 10 mass%, based on the total mass of the grease composition according to the invention.
- The grease composition of the invention further comprises an antioxidant. The antioxidant may include amine type antioxidants, phenol type antioxidants, and the like. In particular, it is recommendable to use the amine type antioxidant and the phenol type antioxidant in combination because the grease tends to deteriorate by oxidation under the circumstances of high temperatures. Examples of the amine type antioxidant include alkyldiphenylamine, N-n-butyl-p-aminophenol, α-naphthylamine, N-phenyl-α-naphthylamine, phenothiazine and the like. In particular, alkyldiphenylamine is preferred. The phenol type antioxidant may include hindered phenols and the like. In particular, hindered phenol is preferred. The total content of the antioxidant may preferably be 0.5 to 6 mass% based on the total mass of the grease composition according to the invention.
- The grease composition of the invention may further comprise other additives, such as other rust inhibitors than the above-mentioned organic sulfonate rust inhibitor, such as amine-based and carboxylate-based rust inhibitors; a metallic corrosion inhibitor such as benzotriazole or the like, an oiliness improver such as fatty acids, fatty acid esters, phosphates and the like; phosphorus-containing, sulfur-containing or organic metal-containing antiwear agent and extreme-pressure agent except the above-mentioned load carrying agent; and a solid lubricant such as oxidized metal salts, molybdenum disulfide or the like. The contents of those optional additives may generally be 0.5 to 5 mass% based on the total mass of the grease composition according to the invention.
- Advantageously, however, the grease composition of the invention may not comprise any nitrite, organic antimony compound or organic molybdenum compound because such compounds contribute to deterioration of the lubrication life at high temperatures. For example, the nitrites include sodium nitrite, the organic antimony compounds include antimony dithiocarbamate and antimony dithiophosphate, and the organic molybdenum compounds include molybdenum dithiocarbamate and molybdenum dithiophosphate.
- The worked penetration of the grease composition according to the invention may preferably be 200 to 300, and more preferably 220 to 280. When the worked penetration exceeds 300, the high-speed revolutions will often cause the problem of grease leakage, which may hinder the satisfactory lubrication life. When the worked penetration is less than 200, the poor flowability of the resultant grease may not satisfy the required lubrication life.
- The bearings where the grease composition of the invention is enclosed are rolling bearings for the automotive electrical equipment or automotive auxiliaries, such as alternators, electromagnetic clutches for car's air conditioners, intermediate pulleys, idler pulleys, tension pulleys and the like.
- Diphenylmethane diisocyanate (MDI) was reacted with an amine (cyclohexylamine (CHA), octylamine and p-toluidine in the predetermined amounts) in each base oil and the reaction mixture was diluted with the base oil to have a worked penetration of 280 (when determined according to JIS K2220), thereby obtaining a base grease. Some additives were added to the base grease. Thus, grease compositions were prepared in Examples and Comparative Examples.
- The base oils and additives used in the preparation of the grease compositions are as follows.
-
- ADE: Alkyldiphenyl ether oil
Alkyl(C12-14) diphenyl ether oil: having a kinematic viscosity at 40°C of 97 mm2/s - POE: Ester oil
Dipentaerythritol ester oil: having a kinematic viscosity at 40°C of 76.9 mm2/s - PAO: Synthetic hydrocarbon oil
Poly(α-olefin) oil: having a kinematic viscosity at 40°C of 68.0 mm2/s - MO: Mineral oil
Naphthenic mineral oil: having a kinematic viscosity at 40°C of 98 mm2/s - The base oil used in Examples 7 and 17 has a kinematic viscosity at 40°C of 92.8 mm2/s: and the base oil used in Examples 8 and 18 has a kinematic viscosity at 40°C of 90.4 mm2/s.
-
- (Organic sulfonate rust inhibitors)
- Ca sulfonate
Ca salt of dinonylnaphthalene sulfonate - Zn sulfonate
Zn salt of dinonylnaphthalene sulfonate
- Ca sulfonate
- (Load carrying additives)
- ZnDTC
Zinc dialkyldithiocarbamate - ZnDTP
Zinc dialkyldithiophosphate
- ZnDTC
-
- Amine type antioxidant
Alkyldiphenylamine - Phenol type antioxidant
Hindered phenol - This test was conducted by rotating the inner ring of a bearing to evaluate the bearing lubrication life at elevated temperatures. The rolling bearing was operated under the following conditions, and the lubrication life was regarded as time duration until the motor caused overcurrent or the bearing temperature increased by 15°C. The results are shown in Tables 1 to 4.
- Bearing type: 6204 metal sealed bearing
- Testing temperature: 180°C
- The number of revolutions: 10,000 rpm
- Test loads:
- axial load 66.7 N
- radial load 66.7 N
- As shown in
Fig. 1 , three steel balls with a diameter of 15 mm designed for bearings were disposed in a cylindrical container with an inner diameter of 40 mm and a height of 14 mm, which was filled with about 20 g of a test grease composition. Another steel ball (5/8-in) for bearing was set to a tester so that the steel ball (5/8-in) was placed in contact with the top of the three steel balls. The steel ball (5/8-in) was driven to rotate for 4 hours for shakedown with the application of a load in a direction of W as shown inFig. 1 , and then hydrogen gas was introduced into the tester. The lower three balls revolved as each rotating on its axis. The ball was driven to rotate continuously until the flaking took place on the steel ball surfaces. - * The flaking occurs at a point between two balls applying the highest contact pressure to each other.
- * The life was expressed as the total number of contact times of the upper ball with the lower balls counted when the flaking took place. These procedures were repeated at least five times to determine the L50 life (i.e., the number of contact times when 50% expired). The results are shown in Tables 1 to 4.
-
- Steel balls for test: 15-mm-dia. steel balls and a 5/8-in steel ball for bearing
- Load for test (W): 100 kgf (4.1 GPa)
- Rotational speed (n): 1500 rpm
- Feed rate of hydrogen gas: 15 ml/min.
- Atmospheric pressure at test part: 0.96 atm. (because of vacuum extraction)
- The repeated number of tests: 5 (at a minimum)
-
- Bearing lubrication life test:
- 600 hours or more: oo (acceptable)
- 500 - 599 hours: o (acceptable)
- less than 500 hours: x (unacceptable)
- Test using four rolling steel balls:
- 20 x 106 times or more: o (acceptable)
- less than 20 x 106 times: x (unacceptable)
- Acceptable in both the bearing lubrication life test and the four rolling steel ball test: o (acceptable)
- Unacceptable in either the bearing lubrication life test or the four rolling steel ball test: x (unacceptable)
[Table 1] Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Thickener Diisocyanate MDI 1 1 1 1 1 1 1 1 1 1 1 (Molar ratio of isocyanate to amine) Monoamine CHA 15 2 1 1.5 1.5 1.5 1.5 1.5 0.8 1.5 1.5 Octylamine 0.5 - 1 0.5 0.5 0.5 0.5 0.5 1.2 0.5 0.5 Base oil ADE 100 100 100 100 100 100 60 60 100 100 100 (Ratio by mass based on 100% base oil) POPE - - - - - - 40 - - - - PAO - - - - - - - 40 - - - Rust inhibitor Zn sulfonate 2.0 2.0 2.0 2.0 - - 2.0 2.0 2.0 2.0 2.0 Ca sulfonate - - - - 2.0 2.0 - - - - - Load carrying additive Zn DTP 1.0 1.0 1.0 - 1.0 - 1.0 1.0 1.0 1.0 1.0 Zn DTC - - - 1.0 - 1.0 - - - - - Antioxidant Amine type 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 - Phenol type 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 - 1.0 Worked penetration 280 280 280 280 280 280 280 280 280 280 280 Seizure life Life (hours) 600< 600< 600< 600< 600< 600< 600< 600< 505 560 532 Evaluation oo oo oo oo oo oo oo oo o o o Test using four rolling steel balls Number of contact times L50 (x106) 20< 20< 20< 20< 20< 20< 20< 20< 20< 20< 20< Evaluation o o o o o o o o o o o Overall evaluation o o o o o o o o o o O * The contents of the rust inhibitor, load carrying additive and antioxidant are represented by mass% based on the total mass of each grease composition. [Table 2] Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 6 Ex. 17 Ex. 18 Ex. 19 Ex. 20 Thickener (Molar ratio of isocyanate to amine) Diiso-cyanate MDI 1 1 1 1 1 1 1 1 1 Monoamine CHA 1.4 1 1.4 1.4 1.4 1.4 1.4 1.4 1.4 p-toluidine 0.6 1 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Base oil (Ratio by mass based on 100% base oil) ADE 100 100 100 100 100 60 60 100 100 POE - - - - - 40 - - - PAO - - - - - - 40 - - Rust inhibitor Zn sulfonate 2.0 2.0 2.0 - - 2.0 2.0 2.0 2.0 Ca sulfonate - - - 2.0 2.0 - - - - Load carrying additive ZnDTP 1.0 1.0 - 1.0 - 1.0 1.0 1.0 1.0 ZnDTC - - 1.0 - 1.0 - - - - Antioxidant Amine type 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 - Phenol type 1.0 1.0 1.0 1.0 1.0 1.0 1.0 - 1.0 Worked penetration 280 280 280 280 280 280 280 280 280 Seizure life Life (hours) 600< 600< 600< 600< 600< 600< 600< 600< 598 Evaluation oo oo oo oo oo oo oo oo o Test using four rolling steel balls Number of contact times L50 (x106) 20< 20< 20< 20< 20< 20< 20< 20< 20< Evaluation o o o o o o o o o Overall evaluation o o o o o o o o o [Table 3] Comp. Ex. 1 Comp. Ex. 2 Comp. Ex. 3 Comp. Ex. 4 Comp. Ex. 5 Comp. Ex. 6 Comp. Ex. 7 Comp. Ex. 8 Comp. Ex. 9 Thickener Diisocyanate MDI 1 1 1 1 1 1 1 1 1 (Molar ratio of isocyanate to amine) Monoamine CHA 1.5 1.5 - 1.5 1.5 1.5 1.5 1.5 15 Octyl-amine 0.5 0.5 2 0.5 0.5 0.5 0.5 0.5 0.5 Base oil (Ratio by mass based on 100% base oil) ADE - - 100 100 100 100 100 100 - POE 100 - - - - - - - - PAO - 100 - - - - - - - MO - - - - - - - - 100 Rust inhibitor Zn sulfonate 2.0 2.0 2.0 2.0 - - - 2.0 2.0 Ca sulfonate - - - - 2.0 - - - - Load carrying additive ZnDTP 1.0 1.0 1.0 - - 2.0 - 1.0 1.0 ZnDTC - - - - - - 2.0 - - Antioxidant Amine type 2.0 2.0 2.0 2.0 2.0 2.0 2.0 - 2.0 Phenol type 1.0 1.0 1.0 1.0 1.0 1.0 1.0 - 1.0 Worked penetration 280 280 280 280 280 280 280 280 280 Seizure life Life (hours) 448 205 333 600< 600< 600< 600< 400 192 Evaluation x x x oo oo oo oo x x Test using four rolling steel balls Number of contact times L50 (x106) 20< 20< 20< 9.8 10.8 10.2 10.5 20< 20< Evaluation o o o x x x x o o Overall evaluation x x x x x x x x x [Table 4] Comp. Ex. 10 Comp. Ex. 11 Comp. Ex. 12 Comp. Ex. 13 Comp. Ex. 14 Comp. Ex. 15 Comp. Ex. 16 Thickener Diisocyanate MDI 1 1 1 1 1 1 1 (Molar ratio of isocyanate to amine) Monoamine CHA 0.6 0.6 0.6 0.6 0.6 0.6 0.6 p-toluidine 1.4 1.4 1.4 1.4 1.4 1.4 1.4 Base oil (Ratio by mass based on 100% base oil) ADE - - 100 100 100 100 100 POE 100 - - - - - - PAO - 100 - - - - - Rust inhibitor Zn sulfonate 2.0 2.0 2.0 - - - 2.0 Ca sulfonate - - - 2.0 - - - Load carrying additive ZnDTP 1.0 1.0 - - 2.0 - 1.0 ZnDTC - - - - - 2.0 - Antioxidant Amine type 2.0 2.0 2.0 2.0 2.0 2.0 - Phenol type 1.0 1.0 1.0 1.0 1.0 1.0 - Worked penetration 280 280 280 280 280 280 280 Seizure Life (hours) 495 252 600< 600< 600< 600< 461 Evaluation x x oo oo oo oo x Test using four rolling steel balls Number of contact times L50 (x106) 20< 20< 7.2 8.4 7.9 8.1 20< Evaluation o o x x x x o Overall evaluation x x x x x x x - The grease compositions of Examples 1 to 20 can exhibit long bearing lubrication life under elevated temperatures, and at the same time excellent resistance to flaking caused by hydrogen embrittlement.
- The grease compositions of Comparative Examples 1, 2 and 9, which are the same as the grease composition of Example 1 except that the ADE is replaced by POE, PAO and MO respectively are all inferior in the seizure life.
- The grease composition of Comparative Example 3 where the diurea thickener does not comprise any cyclohexyl group is inferior in the seizure life.
- The grease compositions of Comparative Examples 4, 5, 12 and 13 containing no load carrying additive, and the grease compositions of Comparative Examples 6, 7, 14 and 15 containing no organic sulfonate rust inhibitor are inferior in the resistance to flaking caused by hydrogen embrittlement in any case.
- The grease compositions of Comparative Examples 8 and 16 containing no antioxidant are inferior in the seizure life.
Claims (10)
- A grease composition for rolling bearings of automotive electrical equipment or automotive auxiliaries, comprising;
a base oil that comprises as an essential component an alkyldiphenyl ether oil;
a thickener consisting of a diurea compound represented by formula (1):
as an anti-flaking additive an organic sulfonate rust inhibitor and a load carrying additive; and
an antioxidant. - The grease composition for rolling bearings of claim 1, wherein the thickener is the diurea compound of formula (1) in which one of R1 or R3 represents cyclohexyl group and the other represents an alkyl group having 8 to 22 carbon atoms, with the ratio of the cyclohexyl group in terms of the number of moles being 50 mol% or more when expressed by [{(the number of cyclohexyl groups) / (the number of cyclohexyl groups + the number of alkyl groups)} x 100].
- The grease composition for rolling bearings of claim 1, wherein the thickener is the diurea compound of formula (1) in which one of R1 or R3 represents cyclohexyl group and the other represents an aromatic hydrocarbon group having 6 to 12 carbon atoms.
- The grease composition for rolling bearings of any one of claims 1 to 3, wherein the organic sulfonate rust inhibitor is represented by formula (2):
[R4-SO3]n1M1 (2)
wherein R4 is an alkyl group, alkenyl group, alkylnaphthyl group, dialkylnaphthyl group, alkylphenyl group or residual group of high-boiling petroleum fraction where the alkyl group or alkenyl group is a straight-chain or branched group having 2 to 22 carbon atoms; M1 is an alkali metal, alkaline earth metal, zinc or ammonium ion; and n1 is the valence number of M1. - The grease composition for rolling bearings of claim 4, wherein the organic sulfonate rust inhibitor is at least one selected from the group consisting of zinc sulfonate and calcium sulfonate.
- The grease composition for rolling bearings of any one of claims 1 to 5, wherein the load carrying additive is at least one selected from the group consisting of thiocarbamates, thiophosphates, naphthenates, carboxylates and organic phosphate esters.
- The grease composition for rolling bearings of any one of claims 1 to 6, wherein the load carrying additive is at least one selected from the group consisting of zinc dialkyldithiocarbamates and zinc dialkyldithiophosphates.
- The grease composition for rolling bearings of any one of claims 1 to 7, wherein the antioxidant is an amine type antioxidant and/or a phenol type antioxidant.
- The grease composition for rolling bearings of claim 8, wherein the amine type antioxidant is an alkyldiphenylamine and the phenol type antioxidant is a hindered phenol.
- A rolling bearing for automotive electrical equipment or automotive auxiliaries, wherein the grease composition of any one of claims 1 to 9 is enclosed.
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JP2012236434A JP6041202B2 (en) | 2012-10-26 | 2012-10-26 | Grease composition |
PCT/JP2013/078950 WO2014065399A1 (en) | 2012-10-26 | 2013-10-25 | Grease composition |
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JP6559983B2 (en) * | 2015-03-18 | 2019-08-14 | Ntn株式会社 | Grease composition |
JP6739951B2 (en) * | 2016-03-11 | 2020-08-12 | 株式会社デンソー | Grease composition, mechanical member and starter overrunning clutch |
JP6700074B2 (en) * | 2016-03-11 | 2020-05-27 | 株式会社デンソー | Grease composition, mechanical member and starter overrunning clutch |
WO2018109128A1 (en) | 2016-12-16 | 2018-06-21 | Castrol Limited | Ether-based lubricant compositions, methods and uses |
JP2019026806A (en) * | 2017-08-03 | 2019-02-21 | Jxtgエネルギー株式会社 | Grease composition |
CN111065717B (en) * | 2017-12-25 | 2024-02-20 | 日本精工株式会社 | Lubricant composition and rolling bearing sealed with the same |
JP7294796B2 (en) * | 2018-11-21 | 2023-06-20 | 協同油脂株式会社 | Grease composition for tapered roller bearings |
JP7522594B2 (en) * | 2020-07-06 | 2024-07-25 | 株式会社ジェイテクト | Grease composition and rolling bearing |
JPWO2022034883A1 (en) * | 2020-08-12 | 2022-02-17 | ||
JP7551473B2 (en) | 2020-11-27 | 2024-09-17 | ミネベアミツミ株式会社 | Anti-oxidation grease composition and bearing containing same |
WO2024161460A1 (en) * | 2023-01-30 | 2024-08-08 | 株式会社ジェイテクト | Grease composition and rolling bearing |
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JP2878749B2 (en) | 1990-01-16 | 1999-04-05 | エヌティエヌ株式会社 | Grease-filled rolling bearings for alternators |
JPH03250094A (en) | 1990-02-28 | 1991-11-07 | Ntn Corp | Grease-filled gearing for electrical equipment and auxiliary machinery of vehicle |
IT1263745B (en) | 1992-01-22 | 1996-08-27 | Ntn Toyo Bearing Co Ltd | CONTACT ROLLING BEARING CLOSED WITH GREASE |
JP2557597B2 (en) | 1992-01-22 | 1996-11-27 | エヌティエヌ株式会社 | Rolling bearing with grease for alternator |
JP2979274B2 (en) * | 1992-06-29 | 1999-11-15 | 日本精工株式会社 | Grease composition for high-speed rolling bearings |
JP3337593B2 (en) * | 1995-06-22 | 2002-10-21 | 日本精工株式会社 | Grease composition for rolling bearings |
JP4620219B2 (en) * | 2000-06-02 | 2011-01-26 | Jx日鉱日石エネルギー株式会社 | Grease composition |
JP2002130301A (en) | 2000-10-17 | 2002-05-09 | Nsk Ltd | Rolling bearing |
US6652149B2 (en) | 2001-02-20 | 2003-11-25 | Nsk Ltd. | Rolling bearing |
JP2002250351A (en) | 2001-02-20 | 2002-09-06 | Nsk Ltd | Rolling bearing |
JP2003013973A (en) * | 2001-06-28 | 2003-01-15 | Ntn Corp | Heat-resistant, high speed, and high-loaded rolling bearing and grease composition |
JP4102627B2 (en) | 2002-09-13 | 2008-06-18 | 株式会社ジェイテクト | Rolling bearing |
JP2004339245A (en) * | 2003-03-18 | 2004-12-02 | Nsk Ltd | Grease composition and rolling apparatus |
JP2005048044A (en) * | 2003-07-28 | 2005-02-24 | Nsk Ltd | Grease composition for rolling apparatus and rolling apparatus |
JP4809793B2 (en) * | 2007-03-08 | 2011-11-09 | 協同油脂株式会社 | Grease composition and machine member |
JP2008239706A (en) * | 2007-03-26 | 2008-10-09 | Kyodo Yushi Co Ltd | Grease composition and bearing |
JP5664890B2 (en) * | 2009-10-15 | 2015-02-04 | 協同油脂株式会社 | Grease composition for wind power generator bearings |
JP5214649B2 (en) * | 2010-02-26 | 2013-06-19 | 協同油脂株式会社 | Grease composition for hub unit bearing using angular ball bearing and hub unit bearing |
JP5774881B2 (en) * | 2011-03-17 | 2015-09-09 | 協同油脂株式会社 | Grease composition |
WO2013015413A1 (en) * | 2011-07-28 | 2013-01-31 | 日本精工株式会社 | Grease composition for ev/hev drive motor bearing, and ev/hev drive motor bearing |
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